Polychlorinated dibenzo-p-dioxins and dibenzofurans in sediment, soil, fish, shellfish and crab samples from Tokyo Bay area, Japan

Polychlorinated dibenzo-p-dioxins and dibenzofurans in sediment, soil, fish, shellfish and crab samples from Tokyo Bay area, Japan

Chemosphere 40 (2000) 627±640 Polychlorinated dibenzo-p-dioxins and dibenzofurans in sediment, soil, ®sh, shell®sh and crab samples from Tokyo Bay ar...

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Chemosphere 40 (2000) 627±640

Polychlorinated dibenzo-p-dioxins and dibenzofurans in sediment, soil, ®sh, shell®sh and crab samples from Tokyo Bay area, Japan Takeo Sakuraia,*, Jong-Guk Kima,1, Noriyuki Suzukib,d, Tomonori Matsuoa, Dong-Qing Lic,d, Yuan Yaoc,d, Shigeki Masunagac,d, Junko Nakanishic,d a

c

Department of Urban Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-8656, Japan b Kanazawa Institute of Technology, 7-1 Ohgigaoka, Nonoichi, Ishikawa 921-8501, Japan Institute of Environmental Science and Technology, Yokohama National University, 79-7 Tokiwadai, Hodogaya, Yokohama, Kanagawa 240-8501, Japan d CREST, Japan Science and Technology Corporation, 4-1-8 Honcho, Kawaguchi 332-0012, Japan Received 11 June 1999; accepted 4 August 1999

Abstract Concentrations of tetra- to octa-chlorinated dibenzo-p-dioxins and dibenzofurans in samples collected in or near Tokyo Bay, Japan, with a densely inhabited catchment area, were congener-speci®cally determined and discussed. Analyzed in this study were samples of surface sediment covering the whole bay area, reference soil representing atmospheric impact, and ®sh, shell®sh and crab commonly consumed as food. The range of concentrations were comparable to or higher than those in other parts of Japan. The origins of these compounds in the catchment area of the bay were investigated in terms of homolog and isomeric compositions in the sediment samples. Biota-sediment accumulation factors for benthic species declined as the degree of chlorination increased. Ó 2000 Elsevier Science Ltd. All rights reserved.

1. Introduction Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are distributed worldwide (Webster and Commoner, 1994). Because some of these compounds exhibit strong toxicity (Webster and Commoner, 1994), they have been a focus of both social and scienti®c concern.

*

Corresponding author. Present address: National Institute for Environmental Studies, 16-2 Onogawa, Tsukuba, Ibaraki 305-0053, Japan. Tel.: +81-298-50-2801; fax: +81-298-50-2570. E-mail address: [email protected] (T. Sakurai). 1 Present address: Faculty of Civil and Environmental Engineering, Chonbuk National University, 664-14 DuckjinDong 1-Ga, Chonju 560-756, South Korea.

As a result of their lipophilic nature, PCDDs and PCDFs accumulate in matrices rich in organic matter, such as soil, aquatic sediment and biota (Webster and Commoner, 1994). Generally, most of these compounds present in the environment will partition into sediment and soil (Mackay et al., 1992). Transformation of these compounds in sediment and soil is considered to be minimal (Webster and Commoner, 1994). Thus sediment and soil will work as conservative matrices which record PCDD and PCDF inputs. In particular, PCDDs and PCDFs that have entered the catchment area via various emissions and routes of environmental transport (e.g., atmospheric or aqueous) will ultimately impact the bay or lake sediment downstream. These matrices are appropriate for overviewing the PCDD and PCDF pollution and their origins in an area. In this paper, the word ÔoriginÕ does not refer to the emission source of

0045-6535/00/$ - see front matter Ó 2000 Elsevier Science Ltd. All rights reserved. PII: S 0 0 4 5 - 6 5 3 5 ( 9 9 ) 0 0 3 2 4 - 0

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T. Sakurai et al. / Chemosphere 40 (2000) 627±640

PCDDs and PCDFs, but to the various inputs of these compounds to environmental matrices. Aquatic organisms such as ®sh, shell®sh and crustaceans are important as the major route of PCDD and PCDF exposure via food to the Japanese population (Takayam et al., 1991a). Food is usually the dominant route of human exposure to these compounds (Birmingham et al., 1989). In addition, the relationship between the PCDD and PCDF concentrations in aquatic organisms and those in aquatic sediment is of interest when estimating human exposure to these compounds. Congener-speci®c data well re¯ect the mixture of PCDD and PCDF input from various origins and are potentially useful in understanding the environmental fate of these compounds (Creaser et al., 1990; Evers et al., 1993; Sakurai et al., 1998). However, only a few congener-speci®c concentrations have been reported in Japan (Yasuhara et al., 1987; Hashimoto and Morita, 1995; Sakurai et al., 1996). We have already measured PCDDs and PCDFs congener-speci®cally in sediment, soil and biological samples from a freshwater lake area in Japan (Sakurai et al., 1996). The PCDD and PCDF concentration data in sediment and soil from the area were analyzed using a multivariate statistical method, and the major origins of these compounds were suggested (Sakurai et al., 1998). In this study, we measure PCDD and PCDF concentrations congener-speci®cally in sediment, soil, ®sh, shell®sh and crab samples from the Tokyo Bay area,

Japan (Fig. 1). The Tokyo Bay area is one of the worldÕs most populous areas with many anthropogenic activities. The ranges of concentrations, homolog and isomeric compositions and their spatial distribution, and biota-sediment accumulation factors will be reported and discussed. A reference soil sample is analyzed, and PCDD and PCDF homolog and isomeric compositions in sediment samples are compared to those in the soil sample in order to obtain information on the origin of these compounds. Biota-sediment accumulation factors for both 2,3,7,8- and non-2,3,7,8-substituted compounds in resident benthic species are calculated using nearby sediment concentrations in order to examine the potential relationship between these matrices. 2. Materials and methods 2.1. Description of the sampling area Tokyo Bay (Fig. 1) is located southeast of Tokyo Metropolitan City, Japan, with its mouth opening to the Paci®c Ocean at the south. Its surface area is 980 km2 , and the catchment area is 7600 km2 , in which 25.6 ´ 106 people reside (Kaizuka, 1993; Ogura, 1993; Environment Agency, 1995). The sea¯oor gradient is generally from shallower northeast to deeper southwest, with an average depth of 15 m and about 50 m maximum (Kaizuka, 1993; Ogura, 1993). Major in¯ow (Edo River,

Fig. 1. Catchment areas of Tokyo Bay and Lake Kasumigaura (left) and sampling sites in Tokyo Bay area (right). X: sediment and soil sampling sites; A-G: Tokyo Bay sediment, Tns: reference soil. O: sampling sites for biological samples; SG: Soga-oki, GI: Goi-oki, AN: Anegasaki-kaigan. BS: Banshu. See Tables 1 and 2 for sample descriptions. Lake Kasumigaura area and the sampling site Ty are included only for reference (see Sakurai et al., 1996). The catchment area map is based on National Institute for Environmental Studies (1991), Ministry of Cconstruction (1995) and Kaizuka (1993).

T. Sakurai et al. / Chemosphere 40 (2000) 627±640

Ara River, Sumida River and Tama River) to the bay is from the north and northwest. The catchment area of 7600 km2 does not include the catchment area of the Tone River which, by splitting its ¯ow, supplies most of the Edo RiverÕs ¯ow. Estimated average water residence time in the bay is 1.6 months (Kaizuka, 1993). Tokyo Bay is considered to be one of the water bodies in Japan most impacted by anthropogenic activities. The catchment area is densely inhabited (33.8 capita/ha), and a wide variety of municipal, agricultural and industrial activities are taking place. Many industrial plants such as oil re®neries and power plants are located along the shoreline. Municipal solid waste incinerators in the area burn more than 6.0 ´ 106 t/yr. Herbicides have been applied to paddy ®elds and other agricultural ®elds which, in all, comprise about 20% of the catchment area (National Land Agency, 1995). All of these activities are probable PCDD and PCDF emission sources (Zook and Rappe, 1994). As the BayÕs sediment was estimated to retain more than 90% of incoming polycyclic aromatic hydrocarbons (PAHs) (Kaizuka, 1993), it is considered suitable to record PCDD and PCDF impact on the bay from the catchment area, because PAHs, and PCDDs and PCDFs have similar physicochemical properties. At the same time, a considerable amount of ®shery activity (more than 20000 t/yr) is ongoing in the bay (Shimizu and Seibutsu, 1997). 2.2. Sampling The sampling sites are shown in Fig. 1. Seven sampling sites were selected to cover Tokyo Bay, and surface sediment samples were collected in May 1995. A surface soil sample (see below) was collected in May 1996. The sampled surface sediments (about 5±10 cm) can be viewed as representing sedimentation of about 10 years before sampling, considering the sedimentation rate (Matsumoto, 1981; Matsumoto, 1983) and surface mixing in the bay. All sediment and soil samples were

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stored in a cool dark place. Information on sediment and soil samples is given in Table 1. Fish, shell®sh and crab samples were collected in May and June 1995 and kept frozen until preparation. Edible portions of the ®sh and crab samples and the whole body, excluding the skin, of a Japanese cockle were subjected to analysis. Information on biological samples is shown in Table 2. The analyzed aquatic organisms are commonly consumed as food in Japan. 2.3. Reference soil sample The soil sample was collected from an experimental plot in the University Farm of the University of Tokyo, Tanashi, Tokyo. This farm is located about 40 km northwest of the bay in a mainly residential area. The plot has been undisturbed since the farm was established at the present site in 1935, and is covered with vegetation of varying density. This plot is considered free from pesticide application (J. Yamagishi, personal communication). Thus, atmospheric deposition is considered to have the main, if not all, impact on the sampled surface soil (5 cm). 2.4. Determination of the PCDD and PCDF concentrations Determination of the PCDD and PCDF concentrations generally followed the method described previously (Sakurai et al., 1996; Kim et al., 1996). Brie¯y, the samples were extracted with organic solvent after addition of 13 C-labeled internal standards. Extracts were treated with concentrated sulfuric acid, and sediment extracts were then treated with copper to remove sulfur. They were then subjected to silica-gel, alumina and activated-carbon puri®cation. The ®nal eluate was congener-speci®cally analyzed for tetra- to octa-chlorinated PCDDs and PCDFs by high-resolution gas chromatography (GC)/high-resolution mass spectrometry (MS). Both DB-5 (5% diphenyl 95% dimethyl polysiloxane,

Table 1 Sampling information and properties of sediment and soil samples Sampling site (sample code) Sediment TB-A TB-B TB-C TB-D TB-E TB-F TB-G Soil Tanashi (Tns) a

Latitude

Longitude

Water depth (m)

Ignition loss (% of dry weight)

35°350 N 35°350 N 35°300 N 35°300 N 35°250 N 35°260 N 35°210 N

139°510 E 139°550 E 139°490 E 139°550 E 139°450 E 139°510 E 139°460 E

11.5 14.0 26.0 23.5 32.0 26.0 20.0

9.70 10.8 11.6 12.1 7.72 10.5 5.91

ÿ

24.1

Tanashi city, Tokyoa

Exact latitude and longitude not available. See Fig. 1 for location.

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T. Sakurai et al. / Chemosphere 40 (2000) 627±640

Table 2 Sampling information and properties of ®sh, shell®sh and crab samples Common name (Japanese) Fish Black rock®sh (mebaru) Olive ¯ounder (hirame) Bartailed ¯athead (kochi)

a b

Scienti®c name

Sampling sitea

Sample code

Body length and weight

Fat contentb

Habitat

Sebastes inermis

BS

BLR

2.5

Inshore ®sh. Has large eyes

Paralichthys olivaceus Platycephalus indicus

AN

OLF

1.2

GI

BFL

16.2 cm 79.3 g 34.2 cm 240 g 51.5 cm 1089 g

Lives in sandy sea bottom Carnivore Lives in clean sandy sea bottom Small ®sh and crustacean eater Cartilaginous ®sh. Benthic shell®sh and crustacean eater Lives inshore in summer and o€shore in winter Swims up river Eats benthos in muddy sediment. Swims up river

0.5

Stingray (akaei)

Dasyatis akajei

SG

STG

38.5 cm 1886 g

2.4

Sea bass (suzuki)

Lateolabrax japonicus

AN

SBS

65.5 cm 2652 g

2.5

Gray mullet (bora)

Mugil cephalus

GI

GRM

55.0 cm 1735 g

4.5

Shell®sh and crab Japanese cockle (torigai)

Fulvia mutica

SG

JCC

5.8 cm 18.6 g

0.5

Crab (ishigani)

Charybdis japonica

GI

CRB

7.7 cm 82.8 g

1.9

Bivalve. Lives in shallow sea bottom. Plankton eater Lives in shallow sea bottom. Small ®sh and shrimp eater

See Fig. 1 for sampling sites. Percent of wet weight.

J&W Scienti®c) and DB-17 (50% phenyl 50% methyl polysiloxane, J&W Scienti®c) were used as the GC stationary phase to enable separation of the seventeen 2,3,7,8-substituted compounds according to previous reports (Sakurai et al., 1996; Kim et al., 1996). In this study, 1,2,3,7,8,9-HxCDF in sediment and soil samples was quantitated on DB-17 because of the better separation. All 87 chromatographic peaks on DB-5, which represent PCDD and PCDF isomers or isomer clusters, were assigned based on relative retention time (Ryan et al., 1991), and quantitated. Detection and quanti®cation followed the criteria set by the US EPA (1994). Isomer or isomer clusters without reference compounds were assumed to have the average recovery and GC/ MS response variation of those with reference compounds. The imprecision of the determined value for sediment and soil samples was estimated to be less than 10% for concentrations greater than 1 pg/g dry weight, and about 10±30% for those less than 1 pg/g dry weight. The same slope was extrapolated out of the calibration curve range for quantitation of some peaks. This usually gives a reasonable quantitation for the injected range in this study. The average recovery of internal standard compounds ranged from 60% to 98%, except

for 13 C12 -1,2,3,4,6,7,8-HpCDF in TB-B, TB-C and TB-F sediment samples. 13 C12 -1,2,3,4,6,7,8-HpCDF showed extraordinarily high recovery (up to 250%) in these three samples and thus was not used for quantitation. The reason for this high recovery is not known. One blank sample was analyzed for every three or four samples. Blank samples gave no or negligible, peaks, except for OCDD in several ®sh and crab samples. The blank OCDD values were subtracted from the ®sh and crab OCDDs. 2.5. Other sample properties Water contents were determined by drying at 105± 110°C for 2 h. Ignition loss, a measure of organic matter content, was determined by heating at 600°C for 1 h after drying. Lipid content was determined by weighing dried extracts after Soxhlet extraction with n-hexane. 3. Results 3.1. PCDD and PCDF concentrations The congener-speci®c concentrations of PCDDs and PCDFs in sediment, soil, shell®sh and crab samples, as

T. Sakurai et al. / Chemosphere 40 (2000) 627±640

determined on DB-5, are shown in Tables 3a,b,c. The total PCDD and PCDF concentrations in the Tokyo Bay sediment samples ranged from 3150 to 20300 pg/g dry weight. The total PCDD and PCDF concentration in the reference soil was 3690 pg/g dry weight. The total PCDD and PCDF concentrations in the shell®sh and crab samples were 1030 and 176 pg/g wet weight, respectively. Values below detection limits were considered to be zero when calculating total concentrations. The concentrations of individual 2,3,7,8-substituted PCDDs and PCDFs and I-TEQ (Kutz et al., 1990) in the sediment, soil, ®sh, shell®sh and crab samples are shown in Table 4. The I-TEQ concentrations in the ®sh, cockle and crab samples ranged from 0.32 to 3.56 pg I-TEQ/g wet weight, with cockle and crab at the higher end. 3.2. Sample properties The determined sample properties are shown in Table 1 for sediment and soil samples, and in Table 2 for biological samples. In this paper, the concentrations in sediment samples were reported without salt correction. With salt correction, the reported values (per dry weight) would be about 15% higher, based on the results from some samples for which water content and salinity of the supernatant water were measured. The concentrations per ignition loss would be the same regardless of salt correction. 4. Discussion 4.1. Concentrations in sediment and soil The total PCDD and PCDF concentration range determined in this study is comparable to those in several other reports for Tokyo Bay sediment, considering the coverage of the sampling sites. The PCDD and PCDF concentrations in surface sediments were reported for the northwestern part of the bay, and their totals ranged about 1700 to 11000 pg/g dry weight (Environment Agency, 1998; Tokyo Metropolitan City, 1994). The concentrations of 2,3,7,8-compounds and the homolog total concentrations were mainly reported. This study is the ®rst to report congener-speci®c concentrations of PCDDs and PCDFs covering the whole area of the bay. The range of total PCDD and PCDF concentrations in the Tokyo Bay sediment samples is higher than in bay sediments from other parts of Japan (Environment Agency, 1998). Generally, the total concentrations in the Tokyo Bay sediment are higher in the eastern sampling sites than their western counterparts, and are also higher in the northern sampling sites. This spatial trend also applies when the concentrations are expressed per ignition loss, a measure of organic matter content. The

631

PCDD and PCDF concentration in the reference soil is in the middle or higher range of the reported values for rural and urban soil from Japan and other countries (Creaser et al., 1989; Creaser et al., 1990; Boss et al., 1992; Osaki et al., 1992; Hashimoto et al., 1999). 4.2. Homolog composition in sediment and soil The homolog compositions of PCDDs and PCDFs in the Tokyo Bay sediment samples resemble each other. OCDD is predominant, and HpCDF and OCDF are the major contributors to the PCDFs (Fig. 2). The dominance of OCDD was also observed in lake sediment which received only atmospheric input (Czuczwa and Hites, 1986). However, contributions from TeCDD and higher chlorinated CDFs, especially OCDF, are greater in Tokyo Bay sediment, probably re¯ecting the impact of other origins. The potential impacts of these origins are later discussed in terms of isomeric composition. The reference soil sample (Tns) can be considered to have received only atmospheric input of PCDDs and PCDFs. The relative contribution of OCDD in this sample (23%) is lower than those in general soil (Creaser et al., 1989; Creaser et al., 1990; Boss et al., 1992; Osaki et al., 1992), another soil sample (Ty) from the Tokyo Bay area (Sakurai et al., 1996), and a lake sediment which received only atmospheric input (Czuczwa and Hites, 1986) (Fig. 2), but close to those in a recent report on soil samples in Japan (Hashimoto et al., 1999). Less chlorinated PCDDs and PCDFs were proposed to be more trapped and to accumulate in vegetation and then deposit to the soil underneath (Horstmann et al., 1997). This mechanism may have contributed to the relatively high contribution from less chlorinated homologs, and also to the relatively high PCDD and PCDF concentration in the Tns soil sample, since the soil was covered with grass and trees. 4.3. Isomeric composition in sediment and soil The isomeric compositions of tetra- to hepta-chlorinated homologs in all sediment samples are generally in agreement with those in the reference soil sample (Tns). This implies that the atmospheric input is one of the major origins of PCDDs and PCDFs over the Tokyo Bay catchment area. Similar isomeric composition was also reported in sediment and soil samples from the Lake Kasumigaura area which is about 75 km northeast of Tokyo Bay (Sakurai et al., 1996; Sakurai et al., 1998). Another soil sample from the Tokyo Bay area (Ty) exhibited an almost identical isomeric composition to that in the Tns soil sample (Sakurai et al., 1996). Interestingly, however, several compounds show remarkably high isomeric contributions in the Tokyo Bay sediment samples compared to the reference soil sample.

1 2 3 4 5 6 7 8 9 10 11 12 13

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

TeCDD

TeCDF

1.000 1.022 1.032 1.048 1.053 1.062 1.077 1.081 1.095 1.106 1.115 1.125 1.136 1.148 1.169 1.180 1.193 1.240

1.000 1.017 1.030 1.061 1.074 1.093 1.108 1.114 1.119 1.128 1.137 1.148 1.171

RRTb

1368 1468 2468 1247/1347/1378/1346/1246e 1247/1347/1378/1346/1246e 1367/1348/1379/1248 1268/1467/1478e 1268/1467/1478e 1369/1237/2368 2467/1238/1236/1469/1678/1234e 2467/1238/1236/1469/1678/1234e 1278 1267/1349 2348/2378/2347/2346/1249/1279 2367 3467/1269 1239 1289

1368 1379 1369 1247/1248/1378/1469 1246/1249/1268/1478 1279 1234/1236/1269 1237/1238 2378 1239 1278 1267 1289

Isomerc

12.5 8.06 21.8 35.0 13.7 24.3 11.8 15.2 32.5 49.6 12.6 12.1 12.5 52.4 25.6 27.4 1.08 0.80

8.13 3.30 26.3 12.5 4.99 19.4 4.10 8.99 10.3 12.1 6.60 7.79 4.93 24.0 7.01 6.62 0.53 0.62

563 243 4.53 7.22 3.15 1.78 2.06 16.9 1.48 0.86 0.83 0.21 0.30

TB-A

Tns 117 70.0 6.49 21.5 9.79 6.13 4.47 10.0 2.27 1.71 3.02 1.12 0.99

Sediment

Soil

5.37 3.57 55.5 12.8 5.08 18.2 4.13 10.5 11.3 13.5 6.36 8.87 5.32 25.2 8.17 6.85 0.56 0.75

1,200 446 10.2 11.8 4.30 2.17 3.23 27.1 0.50 1.16 1.01 <0.25 0.37

TB-B

4.94 3.29 25.9 10.9 4.11 13.6 4.00 7.95 8.53 12.5 6.49 6.35 4.91 20.5 6.32 6.84 0.58 0.88

498 190 4.47 7.25 3.81 1.89 2.34 17.2 0.84 0.91 1.07 0.34 0.38

TB-C

5.60 3.43 43.9 12.6 4.77 15.1 4.55 8.39 10.3 14.1 6.20 6.59 4.76 22.4 7.80 8.43 0.60 0.66

784 303 6.30 9.01 3.99 1.84 2.74 18.8 0.98 1.15 0.84 0.21 0.40

TB-D

b

Without salt correction, see text. Relative retention time (RRT) was calculated to the ®rst eluting peak (isomer or isomer clusters) of each homolog. c Isomer or isomer clusters are listed in the order of elution on DB-5. Peak assignment was based on Ryan et al. (1991). d Detection limits were calculated for a signal-to-noise ratio of 2.5. e Each isomer was assigned to be in either of the two adjacent peaks. f Aggregated with the prior peak.

a

Peak#

Homolog

2.56 1.66 13.1 7.10 2.86 7.26 2.41 4.83 5.24 7.15 3.38 3.44 3.37 11.8 3.76 4.31 0.30 0.32

232 95.8 2.39 4.20 2.28 1.15 1.33 6.36 0.70 0.54 0.64 0.21 0.33

TB-E

2.37 1.64 17.0 7.38 2.73 8.11 2.37 5.29 5.45 7.68 3.53 3.92 3.62 12.4 3.76 4.56 0.30 0.38

371 156 3.55 5.84 3.63 1.51 1.88 9.94 0.63 0.95 0.63 0.21 0.32

TB-F

1.51 1.11 8.25 4.31 1.70 4.60 1.51 2.73 3.29 4.86 2.23 1.83 1.81 7.27 2.19 2.69 0.18 0.17

149 59.8 1.48 2.98 1.60 0.74 0.99 4.79 0.29 0.39 0.50 0.14 0.27

TB-G

2.21 1.31 14.5 4.55 ±f 4.29 3.54 ±f 3.79 6.30 ±f 1.34 1.36 5.76 1.92 1.80 0.19 0.10

266 69.5 1.91 2.58 1.50 0.46 0.86 5.09 0.24 0.28 0.26 <0.15 <0.15

JCC

Shell®sh

1.43 0.097 2.56 2.16 ±f 1.72 0.32 ±f 1.38 1.48 ±f 0.27 0.072 2.43 0.93 0.20 <0.06 <0.06

99.0 11.3 <0.8d 0.98 <0.8 <0.8 <0.8 <0.8 1.60 <0.8 <0.8 <0.8 <0.8

CRB

Crab

Table 3a TeCDD and TeCDF concentrations in soil, sediment, shell®sh and crab samples (pg/g dry weight for soil and sedimenta samples, pg/g wet weight for shell®sh and crab samples) 632 T. Sakurai et al. / Chemosphere 40 (2000) 627±640

*

g

1 2 3 4 5 6 7 8 9 10 11 12

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

PeCDD

PeCDF

1.000 1.049 1.055 1.064 1.072 1.075 1.081 1.085 1.096 1.100 1.109 1.116 1.140 1.148 1.164 1.195

1.000 1.023 1.036 1.043 1.052 1.061 1.065 1.076 1.082 1.093 1.100 1.118

RRTb

Aggregated with the next peak. See Table 3a for other captions.

Peak#

Homolog

13468/12468 13678 12368/12478/13467/13478/12467 13479/14678 12479 13469 23468/12469/12347/12346e 23468/12469/12347/12346e 12348 12378 12367 12678/12379 23478/12489/12679/12369 23467 12349 12389

12468/12479 12469 12368 12478 12379 12369 12467/12489 12347 12346 12378 12367 12389

Isomerc

44.0 10.6 108 15.7 1.60 3.14 34.8 22.0 6.03 15.3 13.4 15.2 26.2 70.3 2.16 1.29

32.7 4.93 40.1 7.50 1.05 1.40 14.2 8.89 3.23 7.85 4.57 7.47 10.9 18.9 1.22 0.90

45.0 3.27 99.3 4.83 37.8 1.77 3.78 4.38 1.07 4.26 1.63 2.08

Tns 107 6.51 44.0 14.7 28.7 5.63 20.0 12.3 3.00 10.2 4.57 4.90

Sediment TB-A

Soil

54.0 4.72 45.7 6.32 1.04 1.78 20.5 10.1 3.63 8.81 5.03 8.18 12.1 19.8 1.18 0.95

63.8 5.05 205 4.20 74.3 2.93 4.78 4.98 1.17 5.22 1.90 2.37

TB-B

90.9 4.79 42.9 6.56 1.12 1.85 17.3 10.6 3.70 7.74 5.33 8.82 12.2 25.5 1.56 1.07

38.5 3.83 87.3 4.00 35.8 2.35 5.17 4.30 1.20 4.46 1.87 2.36

TB-C

67.1 4.71 45.1 6.03 1.27 1.63 22.3 9.83 3.78 9.74 5.83 8.75 13.1 28.1 1.33 1.38

57.9 5.79 173 4.47 65.5 2.84 5.69 4.87 1.22 5.76 2.06 3.62

TB-D

23.9 2.52 23.9 3.66 0.46 0.81 8.32 5.09 1.87 4.56 2.89 4.66 6.23 12.2 0.69 0.52

23.8 2.96 47.0 3.38 18.1 1.18 3.29 2.13 0.58 2.80 1.04 1.59

TB-E

31.0 2.94 29.1 3.76 0.67 1.16 11.0 6.43 2.20 5.29 3.31 5.39 7.45 14.2 0.80 0.61

33.5 3.61 77.2 2.92 30.3 1.58 3.82 2.79 0.75 3.24 1.32 1.71

TB-F

21.5 1.53 14.9 1.94 0.40 0.56 5.72 3.66 1.09 2.60 1.60 2.70 3.91 7.99 0.47 0.30

14.8 2.19 30.5 1.87 11.9 0.88 2.55 1.39 0.39 2.01 0.76 1.17

TB-G

22.7 0.88 8.28 1.53 ±g 0.84 6.47 ±f 0.68 1.66 1.19 1.70 1.73 4.26 0.40 0.20

11.2 1.12 22.5 0.94 6.97 ±g 1.20 0.84 0.23 0.60 0.26 0.30

JCC

Shell®sh

5.30 0.43 2.60 0.28 ±g 0.21 0.89 ±f 0.12 0.37 0.42 0.21 0.90 1.68 <0.06 <0.06

1.92 <0.08d 7.52 0.45 9.28 ±g <0.08 0.27 <0.08 0.24 0.11 <0.08

CRB

Crab

Table 3b PeCDD and PeCDF concentrations in soil, sediment, shell®sh and crab samples (pg/g dry weight for soil and sedimenta samples, pg/g wet weight for shell®sh and crab samples)

T. Sakurai et al. / Chemosphere 40 (2000) 627±640 633

153 43.6 44.5 23.9

3690

1234678 1234679 1234689 1234789

221 189

Total PCDDs +PCDFs

1.000 1.011 1.017 1.061

1234679 1234678

41.2 148 11.6 14.3 7.68 83.7 35.7 8.73 16.8 5.52 67.1 2.72 11.5

9530

502

5850

167 20.1 270 19.7

413 450

21.6 74.1 2.75 6.00 50.1 38.0 16.0 1.63 7.27 4.19 21.9 1.21 4.80

Detection limits for OCDD were calculated based on method blank value. * See Tables 3a and 3b for other captions.

h

1 2 3 4

HpCDF

1.000 1.030

123468 134678/124678 134679 124679 124689 123467/123478 123678 123479 123469/123679 123689 234678 123789 123489

TB-A 50.1 39.3 61.8 2.93 6.82 20.0 17.1

Tns 51.1 87.0 78.3 5.47 11.8 21.8 31.1

139

1 2

HpCDD

1.000 1.007 1.015 1.022 1.030 1.049 1.056 1.061 1.070 1.080 1.083 1.121 1.125

124679/124689 123468 123679/123689 123469 123478 123678 123467/123789

Sediment

Soil

OCDF

1 2 3 4 5 6 7 8 9 10 11 12 13

HxCDF

1.000 1.023 1.035 1.042 1.062 1.066 1.082

Isomerc

857

1 2 3 4 5 6 7

HxCDD

RRTb

OCDD

Peak#

Homolog TB-B

20300

1080

12800

359 16.8 723 30.6

821 1200

36.4 139 2.40 7.69 138 47.7 16.4 1.66 7.37 6.27 22.1 1.21 5.04

75.5 44.7 94.7 5.03 9.70 33.4 25.0

TB-C

10400

522

6150

248 28.1 358 22.9

502 606

29.1 160 3.63 9.44 83.9 43.4 17.7 2.17 8.61 4.71 27.5 1.33 5.56

58.3 40.7 67.3 3.71 7.51 19.8 20.1

TB-D

18200

1050

11600

344 25.0 723 32.1

746 1070

31.3 143 2.74 9.44 140 47.0 19.5 1.72 8.56 7.06 27.0 1.73 5.51

77.4 40.1 87.1 4.04 8.97 32.0 21.5

TB-E

5020

229

3030

88.6 11.7 147 10.3

289 269

13.1 52.4 1.74 4.10 31.8 21.7 8.75 0.87 3.87 2.31 12.5 0.67 2.43

47.1 21.2 41.7 2.10 4.03 10.8 11.9

TB-F

8460

494

5180

150 13.3 300 15.1

424 529

16.6 71.6 1.93 6.01 62.4 27.4 11.0 1.05 4.69 3.29 15.2 0.82 3.17

63.8 29.9 62.4 3.06 5.44 16.8 16.1

TB-G

3150

188

1840

58.0 8.66 96.4 6.81

168 175

8.29 37.6 1.12 3.07 23.4 12.8 5.12 0.67 2.42 1.54 8.22 0.42 1.62

28.8 12.0 25.8 1.22 2.73 7.11 7.85

1030

29.4

315

13.7 1.65 31.8 1.58

28.3 36.7

3.65 17.1 0.58 1.48 17.4 3.92 1.50 0.37 1.51 ±g 3.30 0.13 0.72

5.35 2.35 4.39 0.31 0.66 2.76 0.72

JCC

Shell®sh

176

0.19

<2.58h

0.76 0.07 0.41 <0.06

1.35 1.43

0.59 2.06 0.10 0.22 2.40 0.87 0.37 <0.09 0.23 ±g 0.66 <0.09 <0.09

0.85 0.70 0.87 <0.08d 0.19 0.51 0.17

CRB

Crab

Table 3c HxCDD, HxCDF, HpCDD, HpCDF, OCDD, OCDF and total PCDD + PCDF concentrations in soil, sediment, shell®sh and crab samples (pg/g dry weight for soil and sedimenta samples, pg/g wet weight for shell®sh and crab samples)

634 T. Sakurai et al. / Chemosphere 40 (2000) 627±640

13.2 15.3 20.5 28.3 35.7 67.1 2.61 153 23.9 139

42.8

2378-TeCDF 12378-PeCDF 23478-PeCDF 123478-HxCDF 123678-HxCDF 234678-HxCDF 123789-HxCDF 1234678-HpCDF 1234789-HpCDF 12346789-OCDF

I-TEQe

32.4

8.46 7.85 9.75 20.3 16.0 21.9 1.41 167 19.7 502

1.48 4.26 6.74 20.2 12.5 450 5850

52.3

11.3 8.81 10.4 21.6 16.4 22.1 1.55 359 30.6 1080

0.50 5.28 9.90 36.9 17.5 1200 12800

TB-B

35.6

6.72 7.74 10.8 15.9 17.7 27.5 1.73 248 22.9 522

0.84 4.46 7.87 21.9 13.3 606 6150

TB-C

50.6

7.71 9.74 11.1 31.1 19.5 27.0 1.76 344 32.1 1050

0.98 5.70 8.45 32.4 8.28 1070 11600

TB-D

18.2

3.80 4.56 5.47 11.3 8.75 12.5 0.76 88.6 10.3 229

0.70 2.80 4.26 11.0 9.41 269 3030

TB-E

26.2

4.58 5.29 6.43 11.4 11.0 15.2 1.0 150 15.1 494

0.63 3.24 5.63 18.7 11.0 529 5180

TB-F

11.1

1.94 2.60 3.06 6.77 5.12 8.22 0.52 58.0 6.81 188

0.29 2.01 2.69 6.80 5.67 175 1840

TB-G

Fish

1.16

2.65 0.45 0.89 0.15 0.10 0.26 <0.04 0.05 0.03 0.07

0.18 0.32 0.08 0.24 0.02 0.25 <1.82c

BLR

0.59

0.34 0.18 0.55 0.18 0.15 0.21 0.02 0.12 0.03 0.09

0.10 0.16 0.03 0.24 0.04 0.16 <2.58

OLF

0.32

0.18 0.17 0.19 0.12 0.08 0.14 <0.07 0.24 0.03 0.13

0.07 0.09 <0.02b 0.42 <0.02 0.18 <2.58

BFL

1.84

0.95 0.99 1.28 0.98 0.50 1.13 <0.03 0.60 0.18 0.19

0.20 0.65 0.63 1.30 0.39 3.18 2.46

STG

2.07

3.08 0.77 1.12 0.43 0.24 1.92 <0.03 0.81 0.30 1.61

0.62 0.38 0.09 0.57 0.07 0.62 <1.82

SBS

b

Without the salt correction, see text. Detection limits were calculated for a signal-to-noise rato of 2.5. c Detection limits for OCDD were calculated based on method blank values. OCDD blank values were subtracted for ®sh and crab samples. d The values of 2,3,4,6,7,8-HxCDF in shell®sh and crab samples may include 1,2,3,6,8,9-HxCDF. e TEQ was calculated using I-TEF (Kutz et al., 1990) with values below detection limits set to zero.

a

2.27 10.2 10.4 21.6 19.0 189 857

Sediment

TB-A

Soil

Tns

2378-TeCDD 12378-PeCDD 123478-HxCDD 123678-HxCDD 123789-HxCDD 1234678-HpCDD 12346789-OCDD

Compounds

0.99

1.77 0.63 0.79 0.17 0.09 0.26 <0.07 0.07 0.04 0.10

0.20 0.22 0.03 0.21 <0.02 0.16 <1.82

GRM

3.56

1.50 1.66 1.53 2.82 1.50 3.30d 0.13 13.7 1.58 29.4

0.24 0.60 0.76 2.59 0.47 36.7 315

JCC

Shell®sh

2.56

0.96 0.37 0.91 0.47 0.37 0.66d <0.09 0.76 <0.06 0.19

1.60 0.24 0.22 0.61 0.11 1.43 <2.58

CRB

Crab

Table 4 Concentrations of 2,3,7,8-substituted compounds and TEQs in soil, sediment, ®sh, shell®sh and crab samples (pg/g dry weight for soil and sedimenta samples, pg/g samples, pg/g wet weight for ®sh, shell®sh and crab samples)

T. Sakurai et al. / Chemosphere 40 (2000) 627±640 635

636

T. Sakurai et al. / Chemosphere 40 (2000) 627±640

Fig. 2. Relative homolog concentrations of PCDDs and PCDFs in soil and sediment. Tanashi soil sample (Tns) is considered to have been impacted exclusively by atmospheric input (see text). TB is the average relative concentration of the seven Tokyo Bay samples. Error bars show the range of relative concentrations among the seven sampling sites. Concentrations in Siskiwit Lake sediment, which was reported to have received only atmospheric input, is cited from Czuczwa and Hites (1986).

They include 1,3,6,8-TeCDD, 2,4,6,8-TeCDF, 1,2,3,6,8PeCDD, 1,2,3,7,9-PeCDD, 1,3,4,6,8/1,2,4,6,8-PeCDF, 1,2,4,6,7,9/1,2,4,6,8,9-HxCDD 1,2,4,6,8,9-HxCDF and 1,2,3,4,6,8,9-HpCDF. These compounds may correspond to one or more PCDD and PCDF origins that impacted the catchment area and thus the bay sediments, in addition to atmospheric input. Four major origins of PCDDs and PCDFs in the Lake Kasumigaura area have been suggested, namely, airborne PCDDs and PCDFs, impurities in the herbicide CNP (1, 3, 5-trichloro-2-(4-nitrophenoxy) benzene), impurities in pentachlorophenol, and one unattributed

(Sakurai et al., 1998). The isomers listed above in this study correspond well to those characteristic of these origins (Sakurai et al., 1998), suggesting that these two areas share common origins of PCDDs and PCDFs. 1,3,6,8- and 1,3,7,9-TeCDD are the dominant isomer pair in both sediment samples and reference soil samples. This pair comprises 75% of TeCDDs in the reference soil sample, a similar degree to that in another soil sample from the Tokyo Bay area (Ty) (65%) (Sakurai et al., 1996), and sediment samples from the Korean coast (72%) (Im et al., 1995) and the Baltic Sea (56%) (Kjeller and Rappe, 1995). However, contributions from these two isomers are much higher in sediment samples in this study (about 95%). This high contribution is common in Japanese general sediment samples (Environment Agency, 1998), but not in sediment from other parts of the world, to our knowledge. One of the major contributors to this isomer pair may be impurities in the herbicide CNP (Sakurai et al., 1996; Sakurai et al., 1998; Yamagishi et al., 1981). 4.4. Spatial distribution of isomeric composition Fig. 3 shows the spatial distribution of the relative contribution to the corresponding homolog concentrations from the compounds that showed higher isomeric contribution in sediment samples than in the reference soil sample. It is evident from Fig. 3 that the northeastern sampling sites (TB-B, TB-D) exhibit higher contributions from most of these compounds. This distribution suggests that the impact of origins other than airborne PCDDs and PCDFs is higher in the northeastern part of the bay. The contribution from 1,2,4,6,7,9/1,2,4,6,8,9-HxCDD to the total HxCDDs shows a di€erent distribution and is higher in the southern sampling sites (TB-E, TB-F, TB-G).

Fig. 3. Spatial distribution of isomeric contribution from selected compounds to the corresponding homolog concentrations. Relative isomeric contribution of each compound is normalized among sampling sites between the maximum (outer edge) and minimum (inner edge) contribution. An outer point indicates higher isomeric contribution from the compound, among the Tokyo Bay sampling sites.

T. Sakurai et al. / Chemosphere 40 (2000) 627±640

4.5. PCDD and PCDF accumulation in the bay sediment Based on the average total PCDD and PCDF concentration of 11 ng/g dry weight for the Tokyo Bay sampling sites in this study and the total sedimentation mass of 1.2 ´ 106 t/yr (Matsumoto, 1983), and using the salt correction of 115% (see Sample Properties), a rough total estimation of the PCDD and PCDF accumulation rate in Tokyo Bay sediment is calculated to be about 15 kg/yr. Based on the average PCDD and PCDF concentration of 3.1 pg/l in the bay water (Yamashita et al., 1998) and the estimated water exchange rate of 130 km3 /yr for Tokyo Bay (Kaizuka, 1993), a very rough estimation can be made that the PCDD and PCDF transport rate out of the bay is about 400 g/yr, which is about 37 times less than the estimated accumulation rate in the bay sediment. 4.6. Concentrations in biological samples The I-TEQ concentration range in this study is within or slightly higher than those reported for Japanese coastal ®sh (0.63±1.41 pg/g wet weight) (Takayama et al., 1991b), lake ®sh and shrimp (0.40±2.64 pg/g wet weight) (Sakurai et al., 1996), freshwater and seawater ®sh (0.03±4.5 pg/g wet weight) (Environment Agency, 1998), and ®sh and shell®sh in a background American river (Petreas et al., 1992). When the average Japanese daily intake (MHW, 1996) of 76.3 g for ®sh (including processed ®sh meat), 5.1 g for shell®sh and 15.5 g for crab, squid and octopus are assumed for the ®sh, cockle and crab samples analyzed in this study, respectively, and a body weight of 50 kg is assumed, the estimated daily exposure would range from 1.6 to 4.3 pg I-TEQ/kg body weight. We must note that this estimation is based on a limited number of samples and would be lower if the consumption of generally marketed ®sh were included (Takayama et al., 1991b). Daily PCDD and PCDF

637

intake from ®sh was reported to be 0.47 pg I-TEQ/kg body weight in a recent total diet survey in Japan (MHW, 1998). 2,3,4,7,8-PeCDF is a major contributor to the I-TEQ values in ®sh and shell®sh samples, with 2,3,7,8-TeCDD and 1,2,3,7,8-PeCDD being the second contributor in ®sh samples. 2,3,7,8-TeCDD is the dominant I-TEQ contributor in the crab sample. I-TEQ contribution from 1,2,3,7,8-PeCDD in ®sh, shell®sh and crab samples (4.7±18%) is less than in ®sh and shrimp samples from Lake Kasumigaura (21±36%) (Sakurai et al., 1996). This di€erence in the two areas is also observed in ®sh samples in another report, although a relatively high proportion of the reported values for 2,3,7,8-substituted compounds was below detection limits (Environment Agency, 1998). This di€erence in contribution from 1,2,3,7,8-PeCDD is not discernable between the sediment samples from the two areas (Sakurai et al., 1996; Environment Agency, 1998). The PCDD concentration in the shell®sh sample (790 pg/g wet weight) is higher than the 250 pg/g wet weight of PCDDs in blue mussel (Mitilus edulis) which was the highest from other parts of Japan (Miyata et al., 1987). 1,3,6,8-TCDD alone represents more than half of the total PCDD and PCDF concentration in the crab sample, while 1,3,6,8-TCDD and OCDD, which comprise more than 50% of the total PCDD and PCDF concentration, are the two major compounds in the cockle sample. 4.7. Relationship between PCDDs and PCDFs in benthic organisms and in sediment The isomer composition in the shell®sh sample resembles that in the sediment sample collected nearby (TB-D, see Fig. 1). The crab sample also shows an isomer composition similar to the sediment sample, especially in HxCDD and HxCDF, and to a lesser extent in

Fig. 4. Biota-sediment accumulation factors (BSAFs) of PCDDs and PCDFs in shell®sh and crab samples. BSAFs here are calculated as [pg/g fat]/[pg/g ignition loss]. Sediment TB-D was used to calculated BSAFs. Average BSAF for isomers within each homolog is plotted for both 2,3,7,8- and non-2,3,7,8-substituted compounds. Note that the BSAF axis is logarithmic scale. No points are plotted for octa-chlorinated non-2,3,7,8 compounds because OCDD and OCDF are 2,3,7,8-substituted.

638

T. Sakurai et al. / Chemosphere 40 (2000) 627±640

other homologs. This is probably because they live in a benthic layer with little migration and because they accumulate both non-2,3,7,8- and 2,3,7,8-substituted compounds (Oehme et al., 1989). Thus, the biota-sediment accumulation factor (BSAF ˆ concentration in biological samples [pg/g lipid]/concentration in sediment [pg/g ignition loss]) was calculated for these two samples against the TB-D sediment sample (Fig. 4). Average BSAFs, for both 2,3,7,8-substituted and non-2,3,7,8-substituted isomers within each homolog, decline from 7.2 to 0.66 for cockle and from 10 to 0.0012 for crab as the degree of chlorination increases from 4 to 8. This decline is in accordance with bioconcentration or bioaccumulation factors for aquatic organisms in other reports (Kim et al., 1996; Muir et al., 1985). There is little di€erence in BSAFs between 2,3,7,8- and non-2,3,7,8-substituted compounds and between PCDDs and PCDFs, indicating that these organisms have similar bioaccumulative and metabolic potency for the two groups of compounds, respectively, except for 2,3,7,8-TeCDD in crab. The major contribution from 1,3,6,8-TeCDD to the total PCDD and PCDF concentrations in the crab and cockle samples may be a re¯ection of higher TeCDD BSAF in these organisms and of the dominant isomeric contribution from this isomer in sediment TeCDD. 5. Conclusions The total PCDD and PCDF concentration range in the Tokyo Bay sediment samples was higher than in bay sediments from other parts of Japan. Generally, the total concentrations were higher in the eastern and the northern bay sampling sites. Homolog compositions of PCDDs and PCDFs in the Tokyo Bay sediment samples resembled each other. The isomeric compositions in all sediment samples were generally in agreement with those in the reference soil sample, suggesting that atmospheric input is one of the major origins of PCDDs and PCDFs over the Tokyo Bay catchment area. However, several compounds showed a remarkably higher isomeric contribution in sediment samples than in the reference soil sample. These compounds correspond well to those characteristic of the origins of PCDDs and PCDFs, mainly impurities in herbicides, in an already studied neighboring Lake Kasumigaura area. The northeastern sampling sites in the bay exhibited a higher contribution from most of these compounds than other sampling sites. A rough total estimation of the PCDD and PCDF accumulation rate in the Tokyo Bay sediment was about 15 kg/yr. The range of I-TEQ concentrations in ®sh, shell®sh and crab samples was within or slightly higher than the reported ranges in Japanese aquatic organisms.

2,3,4,7,8-PeCDF was a major contributor to the I-TEQ values in ®sh and shell®sh samples, with 2,3,7,8-TeCDD and 1,2,3,7,8-PeCDD being the second contributor in ®sh samples. The contribution from 1,2,3,7,8-PeCDD in ®sh, shell®sh and crab samples was less than in ®sh and shrimp samples from Lake Kasumigaura. 1,3,6,8-TCDD was the dominant compound in the crab sample, while 1,3,6,8-TCDD and OCDD were the two major compounds in the cockle sample. This isomer composition in the cockle sample, and the crab sample to some extent, resembled that in the sediment sample collected nearby. BSAFs for PCDDs and PCDFs in the cockle and crab samples declined as the degree of chlorination increased from 4 to 8. Little di€erence in BSAFs suggested similar bioaccumulative and metabolic potency in these organisms both for 2,3,7,8-and non-2,3,7,8-substituted compounds and for PCDDs and PCDFs.

Acknowledgements The authors thank Nobuyoshi Yamashita at the National Institute for Resources and Environment, and Junko Yamagishi at University Farm, Faculty of Agriculture, the University of Tokyo, for their help in sampling; and Isamu Ogura for technical discussions and experimental assistance. Part of this study was conducted when one of the authors (TS) was at the Institute of Environmental Science and Technology, Yokohama National University and at the National Institute for Environmental Studies. He thanks both institutes for supporting this study. Financial support by Nippon Life Insurance Foundation, and CREST (Core Research for Evolutional Science and Technology) of the Japan Science and Technology Corporation (JST) is gratefully acknowledged.

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